Probing Bis‐FeIVMauG: Isolation of Highly Reactive Radical Intermediates

Autor:	Sankar Prasad Rath, Tapas Guchhait, Younis Ahmad Pandit, Sabyasachi Sarkar
Rok vydání:	2017
Předmět:	010405 organic chemistry Stereochemistry Diradical Organic Chemistry General Chemistry 010402 general chemistry 01 natural sciences Porphyrin Catalysis 0104 chemical sciences Dication chemistry.chemical_compound chemistry Covalent bond Intramolecular force Moiety Heme Pyrrole
Zdroj:	Chemistry – A European Journal. 23:10270-10275
ISSN:	1521-3765 0947-6539
Popis:	MauG is a diheme enzyme that utilizes two covalently bound c-type heme centers. We report here step-wise oxidations of a synthetic analogue of MauG in which two heme centers are bridged covalently through a flexible linker containing a pyrrole moiety. One- and two-electron oxidations produce monocation radical and dication diradical intermediates, respectively, which, being highly reactive, undergo spontaneous intramolecular rearrangement involving the pyrrole bridge itself to form indolizinium-fused chlorin-porphyrin and spiro-porphyrinato heterodimers. Unlike in MauG, where the two oxidizing equivalents produce the bis-FeIV redox state, the synthetic analogue of the same, however, stabilizes two ferric hemes, each coupled with a porphyrin π-cation radical. The present study highlights the possible role played by the bridge in the electronic communication.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::d2dd48c23d1460c0e9edee8537ebe17f https://doi.org/10.1002/chem.201702321 Zobrazit plný text záznamu Plný text ve formátu PDF Plný text ve formátu HTML
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